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| United States Patent |
6,130,180
|
|
Stewart
, et al.
|
October 10, 2000
|
Catalyst for the polymerization of alpha-olefins containing substituted
amino silane compounds
Abstract
An aminosilane of the formula:
##STR1##
where R.sub.1 is a linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl, which may be substituted with at least one halogen atom;
R.sub.2 is a bis(linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl)amino, a substituted piperidinyl, a substituted pyrrolidinyl,
decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or
1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the
group consisting of C.sub.1-8 alkyl, pheny. C.sub.1-8 linear or branched
alkylsubstituted phenyl and trimethylsilyl, with the proviso that when the
substituent is C.sub.1-8 alkyl, there must be at least two such
substituent groups present and R.sub.1 must contain halogen; and R.sub.3
is a linear or branched C.sub.1-8 alkyl or C.sub.3-8 cycloalkyl. The
aminosilane may be reacted with an aluminum-alkyl compound and a solid
component comprising a titanium compound having at least one
titanium-halogen bond and an electron donor, both supported on an
activated anhydrous magnesium dihalide, to form a catalyst for
polymerization of olefins.
| Inventors:
|
Stewart; Constantine A. (Wilmington, DE);
Evain; Eric J. (Wilmington, DE)
|
| Assignee:
|
Montell North America Inc. (Wilmington, DE)
|
| Appl. No.:
|
996854 |
| Filed:
|
December 23, 1997 |
| Current U.S. Class: |
502/124; 502/119; 502/121; 502/123; 502/125; 502/126; 502/127; 544/229; 546/14; 556/413 |
| Intern'l Class: |
B01J 031/00; C08F 004/656 |
| Field of Search: |
502/119,123,124,125,126,127
528/121
544/229
546/14
556/413
|
References Cited
U.S. Patent Documents
| 4180636 | Dec., 1979 | Hirota et al. | 526/125.
|
| 4242479 | Dec., 1980 | Yokota et al. | 526/124.
|
| 4347160 | Aug., 1982 | Epstein et al. | 252/429.
|
| 4352917 | Oct., 1982 | Tripp | 528/26.
|
| 4382019 | May., 1983 | Greco | 252/429.
|
| 4435550 | Mar., 1984 | Ueno et al. | 526/73.
|
| 4442276 | Apr., 1984 | Kashiwa et al. | 526/125.
|
| 4465782 | Aug., 1984 | McKenzie | 502/104.
|
| 4472524 | Sep., 1984 | Albizzati | 502/113.
|
| 4473660 | Sep., 1984 | Albizzati et al. | 502/124.
|
| 4522930 | Jun., 1985 | Albizzati et al. | 502/124.
|
| 4530912 | Jul., 1985 | Pullukat et al. | 502/104.
|
| 4560671 | Dec., 1985 | Gross et al. | 502/105.
|
| 4581342 | Apr., 1986 | Johnson et al. | 502/119.
|
| 4657882 | Apr., 1987 | Karayannis et al. | 502/115.
|
| 5102842 | Apr., 1992 | Smith et al. | 502/124.
|
| 5401566 | Mar., 1995 | Magee et al. | 428/266.
|
| Foreign Patent Documents |
| 0 045 977 B1 | Feb., 1982 | EP.
| |
| 0 045 976 A2 | Feb., 1982 | EP.
| |
| 0 658 577 B1 | Jun., 1995 | EP.
| |
| 0 841 348 A2 | May., 1998 | EP.
| |
| 7-118320 | May., 1995 | JP.
| |
Primary Examiner: Wood; Elizabeth D.
Claims
What is claimed is:
1. An aminosilane of the following formula:
##STR5##
wherein R.sub.1 is a linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl, which is substituted with at least one halogen atom;
R.sub.2 is a bis(linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl)amino, a substituted piperidinyl, a substituted pyrrolidinyl,
decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or
1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the
group consisting of linear or branched C.sub.1-8 alkyl, phenyl, phenyl
substituted with linear or branched C.sub.1-8 alkyl and trimethylsilyl,
with the proviso that when the substituent is C.sub.1-8 alkyl, there must
be at least two such substituent groups present; and
R.sub.3 is a linear or branched C.sub.1-8 alkyl or C.sub.3-8 cycloalkyl.
2. The aminosilane of claim 1, wherein R.sub.1 is 3,3,3-trifluoro-propyl.
3. The aminosilane of claim 2, wherein R.sub.3 is methyl or ethyl.
4. The aminosilane of claim 3, wherein R.sub.2 is a bis(linear or branched
C.sub.1-22 alkyl or C.sub.3-22 cycloalkyl)amino.
5. The aminosilane of claim 4, wherein R.sub.2 is bis(2-ethylhexyl) amino.
6. The aminosilane of claim 3, wherein R.sub.2 is decahydroquinolinyl.
7. The aminosilane of claim 3, wherein R.sub.2 is
1,2,3,4-tetrahydro-quinolinyl.
8. The aminosilane of claim 3, wherein R.sub.2 is
1,2,3,4-tetrahydro-isoquinolinyl.
9. The aminosilane of claim 3, wherein R.sub.2 is
2-trimethylsilyl-piperidinyl.
10. The aminosilane of claim 3, wherein R.sub.2 is
2-(3-methylphenyl)piperidinyl.
11. The aminosilane of claim 3, wherein R.sub.2 is
cis-2,6-dimethyl-piperidinyl.
12. The aminosilane of claim 3, wherein R.sub.2 is
2-trimethylsilyl-pyrrolidinyl.
13. The aminosilane of claim 3, wherein R.sub.2 is
2-(3-methylphenyl)pyrrolidinyl.
14. A catalyst for the polymerization of olefins, comprising the reaction
product of:
(A) an aluminum alkyl compound;
(B) an aminosilane compound of the formula
##STR6##
wherein R.sub.1 is a linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl, which is substituted with at least one halogen atom;
R.sub.2 is a bis(linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl)amino, a substituted piperidinyl, a substituted pyrrolidinyl,
decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or
1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the
group consisting of linear or branched C.sub.1-8 alkyl, phenyl, phenyl
substituted with linear or branched C.sub.1-8 alkyl and trimethylsilyl,
with the proviso that when the substituent is C.sub.1-8 alkyl, there must
be at least two such substituent groups present must contain halogen; and
R.sub.3 is linear or branched C.sub.1-8 alkyl or C.sub.3-22 cycloalkyl; and
(C) a solid component comprising a titanium compound having at least one
titanium-halogen bond and an electron donor, both supported on an
activated anhydrous magnesium dihalide.
15. The catalyst of claim 14, wherein said aluminum alkyl compound is
triethyl aluminum, and said solid component comprises the reaction product
of titanium tetrachloride, active magnesium chloride and an electron
donor.
16. An aminosilane of the following formula:
##STR7##
wherein R.sub.1 is 3,3,3-trifluoro-propyl;
R.sub.2 is decahydroquinolinyl, 1,2,3,4-tetrahydro-quinolinyl or
1,2,3,4-tetrahydro-isoquinolinyl; and
R.sub.3 is methyl or ethyl.
Description
BACKGROUND OF THE INVENTION
This invention relates to Ziegler-Natta catalyst systems which use an amino
substituted silane electron donor as a co-catalyst component. The olefin
polymers produced with such catalyst systems exhibit a desirable
combination of high isotacticity and high polydispersity index.
The isotacticity of a polymer is important in determining its suitability
for a given application. Isotacticity is often measured by determining the
weight percent of xylene-soluble polymer at room temperature (XSRT) and
subtracting this from one hundred percent. A high isotacticity of greater
than 90 is preferred and greater than 95 is most preferred.
Polydispersity index (P.I.) is a measurement of the molecular weight
distribution of a polymer. A broad molecular weight range distribution (a
high P.I.>4.0) provides improved melt strength, which is advantageous in
thermoforming, film, and fiber formation operations. A high P.I. of 4.0 is
indicative of a broad molecular weight distribution. Preferably the P.I.
is>4.5, most preferably 5.0 or greater.
Organosilane compounds have been used in catalyst systems (1) as an
electron donor in the solid catalyst component comprising a
halogen-containing Ti compound supported on an anhydrous activated
Mg-dihalide compound and (2) as an electron donor with the co-catalyst
component comprising an organometallic compound. Typically they are
organosilane compounds having Si--OR, Si--OCOR or Si--NR.sub.2 bonds,
where R is alkyl, alkenyl, aryl, arylalkyl or cycloalkyl having 1 to 20
carbon atoms and Si as the central atom. Such compounds are described in
U.S. Pat. Nos. 4,180,636; 4,242,479; 4,347,160; 4,382,019; 4,435,550;
4,442,276; 4,465,782, 4,473,660; 4,530,912 and 4,560,671, where they are
used as electron donors in the solid catalyst component; and in U.S. Pat.
Nos. 4,472,524, 4,522,930, 4,560,671, 4,581,342, 4,657,882 and European
patent applications 45976 and 45977, where they are used as electron
donors with the co-catalyst.
U.S. Pat. No. 5,102,842 discloses trifluoropropyl-substituted silanes which
may also contain a piperidinyl or pyrrolidinyl ring, such as
3,3,3-trifluoropropyl (pyrrolidyl)-dimethoxysilane and
3,3,3-trifluoropropyl (4-methylpiperidyl)dimethoxysilane. Even more
recently, European Patent Publication No. 658,577 teaches that fiber
prepared from propylene homopolymers polymerized using
trifluoropropyl(alkyl)dimethoxysilane has a lower bonding temperature and
wider bonding temperature window than fibers of propylene homopolymer
polymerized using catalysts having conventional electron donors such as
phenyltriethoxysilane, dicyclopentyldimethoxysilane and
diphenyldimethoxysilane.
An object of this invention is to provide novel aminosilanes useful as
electron donors in olefin polymerization catalyst systems. Another object
of the invention is to provide an improved catalyst system which produces
olefin polymers having a desirable combination of high isotacticity and
high polydispersity index.
SUMMARY OF THE INVENTION
In one aspect, the present invention relates to aminosilane compounds
conforming to the following formula:
##STR2##
wherein R.sub.1 is a linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl, which may be substituted with at least one halogen atom;
R.sub.2 is a bis(linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl) amino, a substituted piperidinyl, a substituted pyrrolidinyl,
decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or
1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the
group consisting of linear or branched C.sub.1-8 alkyl, phenyl, linear or
branched C.sub.1-8 alkyl substituted phenyl and trimethylsilyl, with the
proviso that when the substituent is C.sub.1-8 alkyl, there must be at
least two such substituent groups present and R.sub.1 must contain
halogen; and
R.sub.3 is a linear or branched C.sub.1-8 alkyl or C.sub.3-8 cycloalkyl.
In a second aspect, the present invention relates to a catalyst for the
polymerization of olefins, comprising the reaction product of:
(A) an aluminum alkyl compound;
(B) aminosilane compounds described above, and
(C) a solid component comprising a titanium compound having at least one
titanium-halogen bond and an electron donor, both supported on an
activated anhydrous magnesium dihalide compound.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As summarized above, the aminosilane compounds of the present invention
conform to the following formula:
##STR3##
wherein R.sub.1 is a linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl, which may be substituted with at least one halogen atom;
R.sub.2 is a bis(linear or branched C.sub.1-22 alkyl or C.sub.3-22
cycloalkyl) amino, a substituted piperidinyl, a substituted pyrrolidinyl,
decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or
1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the
group consisting of linear or branched C.sub.1-8 alkyl phenyl, linear or
branched C.sub.1-8 alkyl substituted phenyl and trimethylsilyl, with the
proviso that when the substituent is C.sub.1-8 alkyl, there must be at
least two such substituent groups present and R.sub.1 must contain
halogen; and
R.sub.3 is a linear or branched C.sub.1-8 alkyl or C.sub.3-8 cycloalkyl.
Preferably, R.sub.1 is 3,3,3-trifluoropropyl, and R.sub.3 is methyl or
ethyl. Illustrative compounds coming within these preferred definitions
include
3,3,3-trifluoropropyl(2-trimethylsilylpiperidinyl)dimethoxysilane;
3,3,3-trifluoropropyl(2-trimethylsilylpyrrolidinyl)dimethoxysilane;
3,3,3-trifluoropropyl(2-(3-methylphenyl)piperidinyl)dimethoxysilane;
3,3,3-trifluoropropyl(2-(3-methylphenyl)pyrrolidinyl)dimethoxysilane;
3,3,3-trifluoropropyl(1,2,3,4-tetrahydroquinolinyl)dimethoxysilane;
3,3,3-trifluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane;
3,3,3-trifluoropropyl(decahydroquinolinyl)dimethoxysilane;
3,3,3-trifluoropropyl(bis(2-ethylhexyl)amino)dimethoxysilane; and
3,3,3-trifluoropropyl(cis-2,6-dimethylpiperidinyl)dimethoxysilane.
The aminosilanes may be prepared by a multistep synthesis route. The first
step is a reaction between the anion from a C.sub.1-22 alkane or
halide-substituted alkane and a commercially available silane such as
tetraalkylorthosilicate (SiOR.sub.4) or tetrachlorosilane. When
tetrachlorosilane is used, an (alkyl)trichlorosilane or
(halide-substituted alkyl)trichlorosilane results. This is converted to
the corresponding (alkyl)trialkoxysilane or (halide-substituted
alkyl)trialkoxysilane by treatment with the appropriate alkoxide (e.g.;
methoxide or ethoxide). When a tetraalkylorthosilicate is used, the
(alkyl)trialkoxysilane or (halide-substituted alkyl)trialkoxysilane is
prepared directly.
The final step is a substitution reaction between the
(alkyl)trialkoxysilane or (halide-substituted alkyl)trialkoxysilane and a
substituted secondary or cyclic amine. The amine-anion is generated by
treatment with either n-butyl lithium or isopropylmagnesium chloride. The
anion is then allowed to react with the (alkyl)trialkoxysilane or
(halide-substituted alkyl)trialkoxysilane to produce the aminosilane.
It is necessary to use a protecting group to prepare certain amines. A
suitable protecting group is tert-butylcarbamate ("BOC") which was used to
prepare 2-trimethylsilylpiperidine, 2-trimethylsilylpyrollidine,
2-(3-methylphenyl)piperidine, and a 2-(3-methylphenyl)pyrrolidine. The BOC
group was attached by generating the anion from either piperidine or
pyrrolidine using sodium hydride in tetrahydrofuran. This solution was
cooled to 5.degree. C. and a slight excess of di-tert-butyldicarbonate
added. After two hours, the solution was poured into saturated sodium
bicarbonate and the layers separated. The organic layer was dried over
magnesium sulfate and the solvent removed by rotary evaporation.
Distillation at reduced pressure provided either
piperidinyl-N-tert-butylcarbamate (bp 95.degree. C., 3 mm Hg, 89% yield)
or pyrrolidinyl-N-tert-butylcarbamate (bp 69.degree. C., 1 mm Hg, 95%
yield).
The aminosilanes of the present invention may be reacted with an aluminum
alkyl compound (A) and a solid component (C) comprising a titanium
compound having at least one titanium-halogen bond and an electron donor,
both supported on an activated anhydrous magnesium dihalide, to form
catalysts suitable for olefin polymerization.
The Al-alkyl compounds forming component (A), which are non-halogen
containing, include: Al-trialkyl, such as Al-triethyl, Al-triisopropyl,
Al-triisobutyl, Al-dialkyl hydrides, such as Al-diethyl hydride, and
compounds containing two or more Al atoms linked to each other through
oxygen, nitrogen or sulfur hetero-atoms, such as:
##STR4##
Preferably, the Al-alkyl compound is Al-triethyl.
In the solid component (C), suitable examples of the titanium compound
having at least a Ti-halogen bond are Ti-tetrahalides, in particular,
TiCl.sub.4. However, alkoxy halides can also be used.
The electron donor compounds employed in component (C) include alkyl, aryl
and cycloalkyl esters of aromatic acids, especially benzoic acid or
phthalic acid and their derivatives. Specific examples include ethyl
benzoate, n-butyl benzoate, methyl p-toluate, diisopropylphthalate,
di-n-butylphthalate, diisobutylphthalate and dioctylphthalate. In addition
to the above esters, alkyl or alkaryl ethers, ketones, mono- or
polyamines, aldehydes and phosphorus compounds, such as phosphines and
phosphoramides, can also be used as the electron donor. The phthalic acid
esters are most preferred.
The active anhydrous magnesium dihalides forming the support of component
(C) are the Mg dihalides showing in the X-ray powder spectrum of component
(C) a broadening of at least 30% of the most intense diffraction line
which appears in the powder spectrum of the corresponding dihalide having
1 m.sup.2 /g of surface area or are the Mg dihalides showing an X-ray
powder spectrum in which said most intense diffraction line is replaced by
a halo with an intensity peak shifted with respect to the interplanar
distance of the most intense line and/or are the Mg dihalides having a
surface area greater than 3 m.sup.2 /g.
The measurement of the surface area of the Mg dihalides is made on
component C) after treatment with boiling TiCl.sub.4 for 2 hours. The
value found is considered as surface area of the Mg dihalide.
The Mg dihalide may be preactivated, may be activated in situ during the
titanation, may be formed in situ from a Mg compound, which is capable of
forming Mg dihalide when treated with a suitable halogen-containing
transition metal compound, and then activated, or may be formed from a Mg
dihalide C.sub.1-3 alkanol adduct wherein the molar ratio of MgCl.sub.2 to
alcohol is 1:1 to 1:3, such as MgCl.sub.2.3ROH.
Very active forms of Mg dihalides are those showing an X-ray powder
spectrum in which the most intense diffraction line appearing in the
spectrum of the corresponding halide having 1 m.sup.2 /g of surface area
is decreased in relative intensity and broadened to form a halo or are
those in which said most intense line is replaced by a halo having its
intensity peak shifted with respect to the interplanar distance of the
most intense line. Generally, the surface area of the above forms is
higher than 30-40 m.sup.2 /g and is comprised, in particular, between
100-300 m.sup.2 /g.
Active forms are also those derived from the above forms by heat-treatment
of component (C) in inert hydrocarbon solvents and showing in the X-ray
spectrum sharp diffraction lines in place of halos. The sharp, most
intense line of these forms shows, in any case, a broadening of at least
30% with respect to the corresponding line of Mg dihalides having 1
m.sup.2 /g of surface area.
Preferred Mg dihalides are MgCl.sub.2 and MgBr.sub.2 and the most preferred
is MgCl.sub.2. The content in water of the halides is generally less than
1% by weight.
By Ti halides or Ti alkoxy halides and electron donors supported on active
Mg dihalide is meant the above compounds which may be chemically or
physically fixed on e support and not extractable from component (C) by
treatment of the same with boiling 1,2-dichloroethane for 2 hours.
Component (C) can be made by various methods. One method consists of
co-grinding the Mg dihalide and the electron donor compound until the
product, after extraction with Al-triethyl under standard conditions,
shows a surface area higher than 20 m.sup.2 g, as set forth above for the
spectrum of the Mg dihalide, and thereafter reacting the round product
with the Ti compound.
Other methods of preparing the solid catalyst component (C) are disclosed
in U.S. Pat. Nos. 4,220,554; 4,294,721; 4,315,835 and 4,439,540, the
methods of which are incorporated herein by reference.
In all of the above methods, component (C) contains a Mg dihalide present
in the active form as set forth above.
Other known methods which lead to the formation of Mg dihalide in active
form or to Ti-containing Mg di-halide supported components, in which the
dihalide is present in active form, are based on the following reactions:
(i) reaction of a Grignard reagent or of a MgR.sub.2 compound (R being a
hydrocarbyl radical) or of complexes of said MgR.sub.2 compounds with Al
trialkyl, with halogenating agents as AlX.sub.3 or AlR.sub.m X.sub.n
compounds (X is halogen, R is a hydrocarbyl, m+n=3), SiCl.sub.4 or
HSiCl.sub.3 ;
(ii) reaction of Grignard compound with a silanol or polysiloxane, H.sub.2
O or with an alcohol and further reaction with a halogenating agent or
with TiCl.sub.4 ;
(iii) reaction of Mg with an alcohol and a halogen halide acid, or of Mg
with a hydrocarbyl halide and an alcohol;
(iv) reaction of MgO with Cl.sub.2 or AlCl.sub.3 ;
(v) reaction of MgX.sub.2.nH.sub.2 O (X=halogen and n is 1-3) with a
halogenating agent or TiCl.sub.4 ; or
(vi) reaction of Mg mono or dialkoxides or Mg carboxylates with a
halogenating agent.
In component (C), the molar ration between the Mg dihalides and the
halogenated Ti compound supported thereon is between 1 and 500 and the
molar ratio between said halogenated Ti compound and the electron donor
supported on the Mg dihalide is between 0.1 and 50.
The catalyst, i.e., components (A), (B) and (C) can be added to the
polymerization reactor by separate means substantially simultaneously,
regardless of whether the monomer is already in the reactor, or
sequentially if the monomer is added to the polymerization reactor later.
It is preferred to premix components (A) and (B), then contact said premix
with component (C) prior to the polymerization for from 3 minutes to about
10 minutes at ambient temperature.
The olefin monomer can be added prior to, with or after the addition of the
catalyst to the polymerization reactor. It is preferred to add it after
the addition of the catalyst.
Hydrogen can be added as needed as a chain transfer agent for reduction in
the molecular weight of the polymer. It is possible to achieve a melt flow
rate of over 1500 g/10 minutes using an appropriate amount of hydrogen and
proper selection of the aminosilane compound. See Example IX below.
The polymerization reactions can be done in slurry, liquid or gas phase
processes, or in a combination of liquid and gas phase processes using
separate reactors, all of which can be done either by batch or
continuously.
The polymerization is generally carried out at a temperature of from
40-90.degree. C. and at atmospheric pressure or at higher pressure.
The catalysts may be precontacted with small quantities of olefin monomer
prepolymerization), maintaining the catalyst in suspension in a
hydrocarbon solvent and polymerizing at a temperature of 60.degree. C. or
below for a time sufficient to produce a quantity of polymer from 0.5 to 3
times the weight of the catalyst.
This prepolymerization also can be done in liquid or gaseous monomer to
produce, in this case, a quantity of polymer up to 1000 times the catalyst
weight.
Suitable alpha-olefins which can be polymerized by this invention include
olefins of the formula CH.sub.2 .dbd.CHR, where R is H or C.sub.1-10
straight or branched alkyl, such as ethylene, propylene, butene-1,
pentene-1,4-methylpentene-1 and octene-1.
The following examples are shown to illustrate the invention and are not
intended to define the scope thereof.
Unless otherwise indicated all parts and percentages in this application
are by weight.
EXAMPLES
Preparation of Electron Donor Compounds
General Procedures:
The purity of all reagents was confirmed by either chromatographic or
spectrophotometric analysis. Where appropriate, reagents were purified
prior to use. All nonaqueous reactions were performed under an atmosphere
of dry nitrogen or argon using glassware that was dried under vacuum while
heated. Air and moisture sensitive solutions were transferred via syringe
or stainless steel cannula. Boiling points and melting points were
uncorrected.
NMR spectra were recorded on a Varian Unity 300 spectrometer operating at
300 MHz and are referenced internally to either tetramethylsilane or
residual proton impurities. Data for .sup.1 H are reported as follows:
chemical shift, (, ppm), multiplicity (s-singlet; d-doublet; t-triplet;
q-quartet; qn-quintet; m-multiplet), integration. Data for .sup.13 C NMR
are reported in terms of chemical shift (.delta., ppm). Infrared spectra
were reported on a BioRad FT430 series mid-IR spectrometer using KBr
plates and are reported in terms of frequency of absorption (v, cm.sup.1).
GC analyses were conducted using a Hewlett Packard model 6890 chromatograph
using flame ionization detection ("FID") coupled to a model HP6890
integrator. In a typical analysis of 1.0 .mu.L was injected into a
250.degree. C. injector (50:1 split ratio; 10 psi column head pressure,
106 mL/min split flow; 111 mL/min total flow). Helium as used as a carrier
gas through an Alltech Heliflex AT-1 column (30 m.times.0.32 mm.times.0.3
m). The initial temperature was held at 50.degree. C. for two minutes then
increased at 10.degree. C./min to a final temperature of 300.degree. C.
The FID detector was held at 300.degree. C. (40 mL/min H.sub.2 ; 400
mL/min air; constant make-up mode using 30 mL/min He).
Two GC/MS systems were used. One system was a Hewlett Packard model 5890 GC
coupled to a Hewlett Packard model 5970 mass selective ("MSD"). In a
typical analysis, 2.0 .mu.L of sample was injected into a 290.degree. C.
splitless injection port. Helium was used as the carrier gas through an
HP-1 (Hewlett Packard, 25 m.times.0.33 mm.times.0.2 .mu.m). The initial
temperature was held at 75.degree. C. for four minutes. The column was
warmed at 10.degree. C./min. MSD acquisition was 10-800 AMU. The spectra
are reported as m/z (relative abundance).
The second GC/MS system was a Hewlett Packard model 6890 GC coupled to a
Hewlett Packard model 5973 mass selective detector. In a typical analysis,
1.0 .mu.L of sample was injected into a 290.degree. C. split/splitless
injection port. Helium was used as the carrier gas through an HP-5
(Hewlett Packard, 30 m.times.0.25 mm.times.0.25 .mu.m). The initial
temperature was held at 50.degree. C. for four minutes. The column was
warmed at 10.degree. C./min. Mass acquisition was 10-800 AMU. The spectra
are reported as m/z (relative abundance).
Example I
3,3,3-Trifluoropropyl(2-trimethylsilylpiperidinyl)dimethoxysilane
2-Trimethylsilylpiperidinyl-N-tert-butylcarbamate--A 1000 mL flask was
charged with piperidinyl-N-tert-butylcarbamate (25.0 g, 135 mmol),
tetramethylethylenediamine ("TMEDA," 44 mL, 290 mmol) and anhydrous ether
(300 mL). The contents were cooled to -78.degree. C. Sec-butyl lithium
(125 mL of 1.3 M solution in cyclohexane, 162 mmol) was added over 25
minutes. The contents were stirred for 3.5 hours while maintaining the
reaction temperature at -78.degree. C. Chlorotrimethylsilane ("TMS-C1",
21.0 mL, 165 mmol) was added over 15 minutes and the contents allowed to
warm to room temperature and stirred for 18 hours. The solution was poured
into dilute hydrochloric acid (400 mL, 0.2 N). The layers were separated
and the organic layer was washed with 0.2 N HCl (3.times.100 mL) and dried
(MgSO.sub.4). Removal of solvent via rotary evaporation provided 53.3 g of
2-trimethylsilylpiperidinyl-N-tert-butylcarbamate: C.sub.13 H.sub.27
NO.sub.2 Si (mw=257.44); MS:m/z (relative abundance) 200 (18.2), 186
(40.2), 156 (47.7), 128 (26.9), 84 (45.5), 73 (100), 57 (87.3).
2-Trimethylsilylpiperidine--A 1000 mL flask was charged with 600 mL ethyl
acetate and chilled to 5.degree. C. Anhydrous hydrogen chloride (>99%) was
bubbled through the ethyl acetate for 15 minutes. The ice bath was removed
and the 2-trimethylsilylpiperidinyl-N-tert-butylcarbamate (107 g, 416
mmol) was added. The solution was stirred for 18 hours. The product was
extracted into water (3.times.200 mL), the layers separated, and the
combined aqueous layers washed with ether (200 mL). The aqueous portion
was brought to pH 14 using 45% (wt/v) potassium hydroxide and extracted
with ether (3.times.150 mL). The combined organic portions were dried
(MgSO.sub.4) and the solvent removed via rotary evaporation. Distillation
at reduced pressure (bp 29.degree. C., 0.5 mmHg) provided
2-trimethylsilylpiperidine (17.0 g, 108 mmol, 26% yield, 97.4% purity by
GC); C.sub.8 H.sub.19 NSi (mw=157.33); .sup.1 H NMR: (CDCl.sub.3) .delta.
3.08 (m, 2H), 2.55 (m, 2H), 2.01 (m, 2H) 1.79 (s, 2H), 1.61-0.80 (m, 11H);
.sup.13 C NMR: (CDCl.sub.3) .delta. 49.0, 48.4, 27.6, 27.0, 26.2, 4.4; IR
(capillary film) v 2926, 2851, 1440, 1258, 1247, 918, 888, 833, 765, 737,
696; MS: m/z (relative abundance) 128 (7.5), 84 (100), 73 (13.8), 56
(17.7), 28 (10.1).
3,3,3-Trifluoropropyl(2-trimethylsilylpiperidinyl)dimethoxysilane--A 500 mL
round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropyl-magnesium chloride (21.5 mL of a 2.0 M solution in THF, 43
mmol). The contents were cooled to 15.degree. C.
2-Trimethylsilylpiperidine (44.5 mmol) was added over fifteen minutes via
pressure equalizing addition funnel. The cold bath was removed and the
contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane
(39.5 mmol) was added via pressure equalizing addition funnel. The
contents were brought to reflux (65-70.degree. C.) for two hours, and
reaction progress was monitored by GC. Isolation was accomplished by
removing the THF via rotary evaporation, taking the residue up in ether
(250 mL), filtration and ether removal via rotary evaporation.
Purification was accomplished by distillation to provide
3,3,3-trifluoropropyl(2-trimethylsilylpiperidinyl)dimethoxysilane (33.5
mmol; 85.0% yield). C.sub.13 H.sub.28 NO.sub.2 SiF.sub.3 (mw=343.53);
.sup.1 H NMR: (CDCl.sub.3) .delta. 3.5 (s, 6H), 3.1-2.9 (m, 1H), 2.8-2.6
(m, 2H), 2.2-2.0 (m, 2H), 1.8-1.35 (m, 5H), 1.32-1.15 (m, 1H), 0.9-0.7 (m,
2H), 0.1 (s, 9H); .sup.13 C NMR: (CDCl.sub.3) 127.7 (quartet J=275 Hz),
50.1, 42.6, 42.2, 28.0 (quartet J=30 Hz), 27.8, 23.4, 3.0, 0.2, -4.2; MS:
m/z (relative abundance) 328 (1.2), 270 (100), 246 (2.2), 155 (6.5), 125
(12.0), 84 (21.5).
Example II
3,3,3-Trifluoropropyl(2-trimethylsilylpyrrolidinyl)dimethoxysilane
2-trimethylsilylpyrrolidinyl-N-tert-butylcarbamate--A 1000 mL flask was
charged with pyrrolidinyl-N-tert-butylcarbamate (23.2 g, 136 mmol),
tetramethylethylenediamine (44 mL, 290 mmol) and anhydrous ether (300 mL),
and cooled to -78.degree. C. Sec-butyl lithium (125 mL of 1.3 M solution
in cyclohexane, 162 mmol) was added over 25 minutes. The reaction contents
were stirred for 3.5 hours while maintaining the temperature at
-78.degree. C. Chlorotrimethylsilane (21.0 mL, 165 mmol) was added over 15
minutes. The contents were allowed to warm to room temperature and stirred
for 18 hours. The solution was poured into dilute hydrochloric acid (750
mL, 0.2 N HCl). The layers were separated and the organic layer was washed
with 0.2 N HCl (3.times.200 mL), brine (1.times.250 mL), and dried
(MgSO.sub.4). Removal of solvent via rotary evaporation provided 93 g of
crude product. Distillation under reduced pressure (85-92.degree. C., 1.8
mmHg) provided 45.9 g (189 mmol, 70% yield) of
2-trimethylsilylpyrrolidinyl-N-tert-butylcarbamate; C.sub.12 H.sub.25
NO.sub.2 Si (mw=243.42).
2-Trimethylsilylpyrrolidine--A 1000 mL flask was charged with 600 mL ethyl
acetate and chilled to 5.degree. C. Anhydrous hydrogen chloride gas (99+%)
was bubbled through the ethyl acetate for 15 minutes. The HCl feed was
stopped, the ice bath removed, and the
2-trimethylsilylpyrrolidinyl-N-tert-butylcarbamate (45.9 g, 189 mmol)
added. The solution was allowed to stir for 18 hours. Water (250 mL) was
added to the solution. The layers were separated and the product was
extracted into water (3.times.200 mL). The aqueous portion was adjusted to
pH 14 using 45% (wt/v) potassium hydroxide. Ether was added (200 mL), the
layers separated, and the aqueous layer extracted into ether (3.times.150
mL). The combined organic portions were dried (MgSO.sub.4) and the solvent
removed via rotary evaporation. Distillation at reduced pressure
(25.degree. C., 1.5 mmHg) provided 2-trimethylsilylpyrrolidine (16.0 g,
112 mmol, 64% yield, >99% purity); C.sub.17 H.sub.11 NSi (mw=143.30);
.sup.13 C NMR: .delta. 49.0, 48.9, 28.1, 26.7, -3.3, -3.6, -4.0; IR
(capillary film) v 2952, 2866, 2823, 2752, 1423, 1247, 1069, 936, 892,
837, 747, 692, 622; MS: m/z (relative abundance) 115 (11.9), 100 (14.9),
73 (10.0), 70 (100), 43 (12.4), 28 (13.2).
3,3,3-Trifluoropropyl(2-trimethylsilylpyrrolidinyl)dimethoxysilane--A 500
mL round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropyl-magnesium chloride (28.25 mL of a 2.0 M solution in THF, 56.5
mmol). The contents were cooled to 15.degree. C.
2-Trimethylsilylpyrrolidine (58.0 mmol) was added over fifteen minutes via
pressure equalizing addition funnel. The cold bath was removed and the
contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane
(51.3 mmol) was added via pressure equalizing addition funnel. The
contents were brought to reflux (65-70.degree. C.) for two hours, and
reaction progress was monitored by GC. Isolation was accomplished by
removing the THF via rotary evaporation, taking the residue up in ether
(250 mL), filtration and ether removal via rotary evaporation.
Purification was accomplished by distillation to provide
3,3,3-trifluoropropyl(2-trimethylsilylpyrrolidinyl)dimethoxysilane (46.7
mmol; 91% yield). C.sub.12 H.sub.26 NO.sub.2 Si.sub.2 F.sub.3 (mw=329.51);
.sup.1 H NMR: (CDCl.sub.3) .delta. 3.50 (s, 3H), 3,45 (s, 3H), 3.25-3.10
(m, 1H), 2.90-2.80 (m, 1H), 2.80-2.65 (m, 1H), 2.20-1.50 (m, 6H),
0.85-0.75 (m, 2H), -0.05 (s, 9H); .sup.13 C NMR: (CDCl.sub.3) .delta.
129.6 (quartet J=275), 50.1, 49.0, 47.6, 46.7, 28.2 (quartet J=30), 28.0,
27.5, 2.9, -2.7; .sup.29 Si NMR: (CDCl.sub.3) .delta. 2.07, -34.74; MS:
m/z (relative abundance) 314 (1.5), 256 (100), 232 (1.7), 155 (3.8), 125
(3.6) 70 (4.2).
Example III
3,3,3-Trifluoropropyl(2-(3-methylphenyl)-piperidinyl)dimethoxysilane
(2-(3-Methyiphenyl)piperidinyl)-N-tert-butylcarbamate--A 500 mL flask was
charged with piperidinyl-N-tert-butylcarbamate (18.5 g, 100.times.10.sup.2
mmol), tetramethylethylenediamine (33 mL, 220 mmol), and THF (200 mL). The
contents were cooled to -78.degree. C. Sec-butyl lithium (93 mL of 1.3 M
solution in cyclohexane, 120 mmol) was added over 15 minutes. The reaction
was stirred at -78.degree. C. for 3.5 hours. A 1000 mL flask was charged
with THF (200 mL), 3-iodotoluene (25.7 mL, 2.00.times.10.sup.2 mmol),
copper(I) cyanide (0.896 g, 1.00.times.10.sup.2 mmol), and
bis(triphenylphosphine)palladium chloride (3.5 g, 5.0 mmol). The contents
were cooled to -78.degree. C. The piperidinyl-N-tert-butylcarbamate anion
was transferred into the iodotoluene solution via cannula. The reaction
was allowed to stir for 18 hours and then heated to reflux (75.degree. C.)
for another 18 hours. The cooled contents were added to water (200 mL),
the layers separated, and the aqueous layer extracted with ether
(2.times.150 mL). The combined organic portions were washed with brine
(3.times.150 mL) and dried (MgSO.sub.4). Removal of solvent by rotary
evaporation provided 59.5 g of crude
2-(3-methylphenyl)-piperidinyl-N-tert-butylcarbamate. C.sub.17 H.sub.25
NO.sub.2 (mw=275.39); MS: m/z (relative abundance) 275 (0.3), 219 (73.0),
202 (12.4), 174 (97.3), 158 (34.8), 146 (20.6), 132 (14.6), 57 (100).
2-(3-Methylphenyl)piperidine--A 1000 mL flask was charged with ethyl
acetate 600 mL) and chilled to 5.degree. C. Anhydrous hydrogen chloride
gas (99%) was bubbled through the ethyl acetate for 15 minutes. The HCl
feed was stopped, the ice bath removed, and the
2-(3-methylphenyl)piperidinyl-N-tert-butylcarbamate (59.5 g, 216 mmol)
added. The solution was allowed to stir for 18 hours. Water (250 mL) was
added to the solution. The layers were separated and the product was
extracted into water (3.times.200 mL). The aqueous portion was adjusted to
pH 14 with 45% (wt/v) potassium hydroxide. The product was extracted into
ether (4.times.150 mL). The combined organic portions were dried
(MgSO.sub.4) and the solvent removed via rotary evaporation. Distillation
under reduced pressure (75-90.degree. C., 0.3 mmHg) provided
2-(3-methylphenyl)piperidine (10.4 g, 59.3 mmol, 27.5% yield); C.sub.12
H.sub.17 N (mw=175.27); .sup.1 H NMR: .delta.(CDCl.sub.3) 7.2-7.0 (m, 4H),
3.5 (m, 1H), 3.1 (m, 1H), 3.7 (t, 1H), 2.3 (s, 3H), 1.9-1.4 (m, 7H):
.sup.13 C NMR: .delta.(CDCl.sub.3) 145.4, 137.6, 128.0, 127.5, 127.0,
123.5, 62.1, 47.6, 34.8, 25.6, 25.3, 21.1; IR (capillary film) v 3319,
3267, 3022, 2924, 1932, 1855, 1777, 1680, 1441, 1323, 1108, 783, 701; MS:
m/z (relative abundance) 175 (35.7), 160 (10.4), 146 (45.0), 132 (34.6),
118 (100), 91 (31.7)84 (48.4), 56 (7.7), 28 (23.3).
3,3,3-Trifluoropropyl(2-(3-methylphenyl)piperidinyl)dimethoxysilane--A 500
mL round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropylmagnesium chloride (15 mL of a 2.0 M solution in THF, 30 mmol).
The contents were cooled to 15.degree. C. 2-(3-Methylphenyl)piperidine
(34.3 mmol) was added over fifteen minutes via pressure equalizing
addition funnel. The cold bath was removed and the contents stirred for
two hours. 3,3,3-Trifluoropropyltrimethoxysilane (31.1 mmol) was added via
pressure equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours, and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide
3,3,3-trifluoropropyl(2-(3-methylphenyl)-piperidinyl)dimethoxysilane (24.1
mmol; 80.4% yield; b pt 101.degree. C. at 0.2 mm Hg). C.sub.17 H.sub.26
NO.sub.2 SiF.sub.3 (mw=361.47); MS: m/z (relative abundance) 361 (13.4),
332 (3.6), 270 (100), 174 (5.6), 155 (9.1), 125 (12.0), 105 (12.2), 59
(19.4).
Example IV
3,3,3-Trifluoropropyl(2-(3-methylphenyl)-pyrrolidinyl)dimethoxysilane
(2-(3-Methylphenyl)-pyrrolidinyl)-N-tert-butylcarbamate--A 500 mL flask
was charged with pyrrolidinyl-N-tert-butylcarbamate (17.3 g, 101 mmol),
tetramethylethylenediamine (33 mL, 220 mmol), and THF (200 mL). The
contents were cooled to -78.degree. C. Sec-butyl lithium (93 mL of 1.3 M
solution in cyclohexane, 120 mmol) was added over 15 minutes and the
contents stirred at -78.degree. C. for 3.5 hours. A 1000 mL flask was
charged with THF (200 mL), 3-iodotoluene (25.7 mL, 7.00.times.10.sup.2
mmol), copper(I) cyanide (0.896 g, 10.0 mmol), and
bis-(triphenylphosphine)palladium chloride (3.5 g, 5.0 mmol). The contents
were cooled to -78.degree. C. The piperidinyl-N-tert-butylcarbamate anion
was transferred into the iodotoluene solution via cannula. The reaction
was allowed to stir for 18 hours and then heated to reflux (75.degree. C.)
for 18 hours. The contents were cooled and added to water (200 mL). The
layers were separated and the aqueous layer was extracted with ether
(2.times.150 mL). The combined organic portions were washed with brine
(3.times.150 mL) and dried (MgSO.sub.4). Removal of solvent by rotary
evaporation provided 62.5 g of crude product. Distillation under reduced
pressure (145.degree. C., 0.2 mmHg) provided
2-(3-methylphenyl)pyrrolidinyl-N-tert-butylcarbamate (13.3 g, 50.9 mmol,
50% yield): C.sub.16 H.sub.23 NO.sub.2 (mw=261.36).
2-(3-Methylphenyl)pyrrolidene--A 1000 mL flask was charged with ethyl
acetate (600 mL) and chilled to 5.degree. C. Anhydrous hydrogen chloride
gas (99%) was bubbled through the ethyl acetate for 15 minutes. The HCl
feed was stopped, the ice bath removed and the
2-(3-methylphenyl)pyrrolidinyl-N-tert-butylcarbamate (35.0 g, 134 mmol)
was added. The solution was allowed to stir for 18 hours. Water (250 mL)
was added, the layers separated, and the product extracted into water
(3.times.200 mL). The aqueous portion was adjusted to pH 14 using 45%
(wt/v) potassium hydroxide. The product was extracted into ether
(4.times.150 mL). The combined organic portions were dried (MgSO.sub.4)
and the solvent removed via rotary evaporation. Distillation under reduced
pressure (115-122.degree. C., 2 mmHg) provided a 70:30 mixture of
2-(3-methylphenyl)-pyrrolidine and 2-(3-methylphenyl)pyrrolidene (14 g,
65% yield).
2-(3-Methylphenyl)pyrrolidine--A pressure reactor was charged with the
olefin/product mixture (14 g), absolute ethyl alcohol (140 mL) and
platinum oxide (2.8 g, 12 mmol). The reactor was filled with hydrogen
(99.99%) to a pressure of 50 psig. The reaction mass stirred for 18 hours
during which time the pressure decreased to 3 psig. The ethyl alcohol was
removed by distillation under nitrogen. Distillation of the remainder
under reduced pressure (63-74.degree. C., 0.1 mmHg) provided
2-(3-methylphenyl)-pyrrolidine (10.8 g, 67 mmol, 77% yield, 97% purity);
C.sub.11 H.sub.15 N (mw=161.24); .sup.1 H NMR: .delta.(CDCl.sub.3) 7.3-6.9
(m, 4H), 4.1 (t, 1H), 3.1 (m, 1H), 2.9 (m, 1H), 2.3 (s, 3H), 2.1 (m, 1H),
1.9 (m, 3H), 1.6 (m, 1H); .sup.13 C NMR: .delta.(CDCl.sub.3) 144.9, 137.9,
128.2, 127.5, 127.2, 123.6, 62.6, 47.0, 34.3, 25.6, 21.4; IR (capillary
film) v 3327, 3014, 2953, 2866, 1937, 1861, 1783, 1399, 781, 709, MS: m/z
(relative abundance) 160 (62.9), 146 (40.5), 132 (100), 118 (92.6), 92
(25.2), 70 (45.3), 43 (6.0), 28 (14.8).
3,3,3-Trifluoropropyl(2-(3-methylphenyl)pyrrolidinyl)dimethoxysilane--A 500
mL round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropyl-magnesium chloride (20 mL of a 2.0 M solution in THF, 40 mmol).
The contents were cooled to 15.degree. C. 2-(3-Methylphenyl)pyrrolidine
(39.1 mmol) was added over fifteen minutes via pressure equalizing
addition funnel. The cold bath was removed and the contents stirred for
two hours. 3,3,3-Trifluoropropyltrimethoxysilane (36.3 mmol) was added via
pressure equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours, and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide
3,3,3-trifluoropropyl(2-(3-methylphenyl)-pyrrolidinyl)dimethoxysilane
(24.3 mmol; 62.2% yield). C.sub.16 H.sub.24 NO.sub.2 SiF.sub.3 (mw=347.45)
bp=128.degree. C. at 0.2 mmHg; .sup.1 H NMR: (CDCl.sub.3) .delta. 7.3-6.9
(m, 4H), 4.5 (t, 1H), 3.41 (s, 3H), 3.40 (s, 3H), 3.3 (t, 2H), 2.3 (s,
3H), 2.2-2.1 (m, 2H), 2.0-1.7 (m, 4H), 1.7-1.6 (m, 2H); .sup.13 C NMR:
(CDCl.sub.3) .delta. 147.8, 137.7, 128.1, 127.6 (quartet, J=275.9 Hz),
127.2, 126.8, 123.2, 61.7, 50.3, 47.4, 37.0, 34.3, 27.7 (quartet, J=30.1
Hz) 21.4, 3.0: MS: m/z (relative abundance) 347 (18.0), 318 (8.3), 304
(3.7), 256 (100), 155 (12.0), 125 (15.9), 59 (24.6).
Example V
3,3,3-Trifluoropropyl(cis-2,6-dimethylpiperidinyl)dimethoxysilane
cis-2,6-Dimethylpiperidine--A 1000 mL round-bottomed flask was charged
with 5M KOH (600 mL, 3 moles) and lutidine (15.0 g, 1.50.times.10.sup.2
mmol). A solid aluminum/nickel alloy was added over 48 hours (1200 g).
During the addition of the alloy, gas evolved and the internal temperature
increased from 35.degree. C. to 65.degree. C. (no more than 15 g of the
alloy was added in one portion). The salts were filtered through
celite.sup.1, and the filter cake washed with ether and water. The layers
were separated. The product was extracted into ether (3.times.150 mL) and
dried (MgSO.sub.4), leaving crude 2,6-dimethylpiperidine (8.13 g, 71.2
mmol, 51% yield).
.sup.1 CAUTION: A flammable Raney nickel type solid remains in the celite.
This material will ignite in air if the filter cake dries. The solid is
best neutralized by stirring it in a generous amount of dilute nitric acid
for 48 hours.
3,3,3-Trifluoropropyl(cis-2,6-dimethylpiperidinyl)dimethoxysilane--A 500 mL
round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropyl-magnesium chloride (31 mL of a 2.0 M solution in THF, 62 mmol).
The contents were cooled to 15.degree. C. Cis-2,6-dimethylpiperidine (64
mmol) was added over fifteen minutes via pressure equalizing addition
funnel. The cold bath was removed and the contents stirred for two hours.
3,3,3-Trifluoropropyltrimethoxysilane (57 mmol) was added via pressure
equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours, and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide 3,3,3-trifluoropropyl(cis-2,6-dimethylpiperidinyl)dimethoxysilane
(27.4 mmol; 48% yield). C.sub.12 H.sub.24 NO.sub.2 SiF.sub.3 (mw=299.40)
bp=66.degree. C. at 0.3 mmHg; .sup.1 NMR: (CDCl.sub.3) .delta. 3.5 (s,
6H), 3.4-3.3 (m, 2H), 2.2-2.0 (m, 2H), 1.9-1.7 (m, 1), 1.6-1.4 (m, 5H),
1.2-1.0 (m, 6H), 0.8-0.7 (m, 2H); .sup.13 C NMR: (CDCl.sub.3) .delta. 128
(quartet, J=275 Hz), 50.1, 44.2, 31.6, 28.3 (quartet, J=30 Hz), 24.6,
20.5, 14.3:MS: m/z (relative abundance) 299 (0.7), 284 (100), 202 (6.7),
155 (7.9), 98 (12.7), 59 (12.5).
Example VI
3,3,3-Trifluoropropyl(1,2,3,4-tetrahydroquinolinyl)dimethoxysilane--A 500
mL round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropyl-magnesium chloride (30 mL of a 2.0 M solution in THF, 60 mmol).
The contents were cooled to 15.degree. C. 1,2,3,4-Tetrahydroquinoline (60
mmol) was added over fifteen minutes via pressure equalizing addition
funnel. The cold bath was removed and the contents stirred for two hours.
3,3,3-Trifluoropropyltrimethoxysilane (54.5 mmol) was added via pressure
equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide 3,3,3-trifluoropropyl(1,2,3,4-tetrahydroquinolinyl)dimethoxysilane
(54 mmol; 99% yield). C.sub.14 H.sub.20 NO.sub.2 SiF.sub.3 (mw=319.39)
bp=110.degree. C. at 0.35 mmHg; .sup.1 H NMR: (CDCl.sub.3) .delta. 7.1-6.4
(m, 4H), 3.6-3.2 (m, overlapping with singlet, 8H), 2.9-2.7 (m 2H),
2.2-1.7 (m, 4H), 1.3-0.7 (m, 2H); .sup.13 C NMR: (CDCl.sub.3) .delta.
130.2, 129.6, 128 (quartet, J=275 Hz), 126.8, 126.5, 119.2, 117.0, 50.5,
43.5, 27.8 (quartet, J=30 Hz), 23.8, 22.4, 3.4; MS: m/z (relative
abundance) 319 (100), 222 (11.7), 190 (6.5), 182 (6.2) 155 (10.7), 132
(55.0), 125 (21.8), 117 (12.1), 59 (32.6).
Example VII
3,3,3-Tritluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane--A
500 mL round bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropyl-magnesium chloride (30 mL of a 2.0 M solution in THF, 60 mmol).
The contents were cooled to 15.degree. C. 1,2,3,4-Tetrahydroisoquinoline
(60 mmol) was added over fifteen minutes via pressure equalizing addition
funnel. The cold bath was removed and the contents stirred for two hours.
3,3,3-Trifluoropropyltrimethoxysilane (54.5 mmol) was added via pressure
equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide
3,3,3-trifluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane (54
mmol; 99% yield). C.sub.14 H.sub.20 NO.sub.2 SiF.sub.3 (mw=319.39)
bp=98.degree. C. at 0.3 mmHg; .sup.1 H NMR: (CDCl.sub.3) .delta. 7.2-6.9
(m, 4H), 4.2-4.0 (d, 2H), 3.6-3.4 (s, 6H), 3.3-3.1 (dt, 2H), 2.8-2.6 (m,
2H), 2.2-1.9 (m, 2H), 0.9-0.8 (m, 2H); .sup.13 C NMR: (CDCl.sub.3) .delta.
135.9, 135.1, 129.4, 128 (quartet J=275 Hz), 126.0, 125.9, 125.8, 50.4,
46.5, 42.1, 29.9, 28 (quartet, J=30 Hz), 2.8; MS: m/z (relative abundance)
319 (38.3), 318 (100), 222 (7.9), 132 (21.0), 104 (21.4), 79 (9.8), 59
(13.4).
Example VIII
3,3,3-Trifluoropropyl(decahydroquinolinyl)dimethoxysilane--A 500 mL round
bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropylmagnesium chloride (28.75 mL of a 2.0 M solution in THF, 57.5
mmol). The contents were cooled to 15.degree. C. Decahydroquinoline (57.5
mmol) was added over fifteen minutes via pressure equalizing addition
funnel. The cold bath was removed and the contents stirred for two hours.
3,3,3-Trifluoropropyltrimethoxysilane (52.3 mmol) was added via pressure
equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours, and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide 3,3,3-trifluoropropyl(decahydroquinolyinyl)dimethoxysilane (53.1
mmol; quantitative yield). C.sub.14 H.sub.26 NO.sub.2 SiF.sub.3
(mw=325.44) bp=103.degree. C. at 1.0 mmHg; .sup.1 H NMR: (CDCl.sub.3)
.delta. 3.5 (s, 6H), 3.1-2.7 (m, 3H), 2.2-1.9 (m, 3H), 1.8-1.1 (m, 12H),
0.9-0.7 (m, 2H); .sup.13 C NMR (CDCl.sub.3) .delta. 127.9 (quartet, J=275
Hz), 52.6, 50.4, 38.2, 36.9, 29.0, 28.5, 27.8 (quartet, J=30 Hz), 26.4,
26.3, 20.5, 3.1; MS: m/z (relative abundance) 325 (14.3), 282 (100), 228
(4.1), 125 (6.8), 96 (11.3), 59 (12.6).
Example IX
3,3,3-Trifluoropropyl(bis(2-ethylhexyl)aminodimethoxysilane--A 500 mL round
bottomed flask was charged with tetrahydrofuran (300 mL) and
isopropylmagnesium chloride (25 mL of a 2.0 M solution in THF, 50 mmol).
The contents were cooled to 15.degree. C. Bis(2-ethylhexyl)amine (50 mmol)
was added over fifteen minutes via pressure equalizing addition funnel.
The cold bath was removed and the contents stirred for two hours.
3,3,3-Trifluoropropyltrimethoxysilane (45 mmol) was added via pressure
equalizing addition funnel. The contents were brought to reflux
(65-70.degree. C.) for two hours, and reaction progress was monitored by
GC. Isolation was accomplished by removing the THF via rotary evaporation,
taking the residue up in ether (250 mL), filtration and ether removal via
rotary evaporation. Purification was accomplished by distillation to
provide 3,3,3-trifluoropropyl bis(2-ethylhexyl)aminodimethoxysilane (44
mmol; 98% yield). C.sub.21 H.sub.44 NO.sub.2 SiF.sub.3 (mw=427.66)
bp=200.degree. C. at 1.4 mmHg; .sup.1 H NMR: (CDCl.sub.3) .delta. 3.5 (s,
6H), 2.6-2.4 (dd, 4H), 2.2-2.0 (m, 2H), 1.6-1.1 (m, 18H), 1.0-0.7 (m,
14H); .sup.13 C NMR: (CDCl.sub.3) .delta. 128 (quartet, J=275 Hz), 50.4,
48.5, 39.4, 36.9, 30.8, 29.1, 28.2 (quartet, J=30 Hz), 23.2, 14.2, 10.3,
3.2; MS: m/z (relative abundance) 328 (100), 230 (25.6), 155 (7.4), 109
(2.9).
Example X
Polymerization Procedure
The aminosilane compounds of Examples I-IX were used as electron donors to
polymerize propylene monomer. The polymerization reactor was heated to
70.degree. C. and purged with a slow argon flow for 1 hour. The reactor
was then pressurized up to 100 psig with argon at 70.degree. C. and then
vented. This procedure was repeated 4 more times. The reactor was then
cooled to 30.degree. C.
Separately, into an argon purged addition funnel was introduced in the
following order: 75 mL of hexane, 4.47 mL of 1.5 M solution of
triethylaluminum (TEAL) (0.764 g, 0.0067 mol) in hexane, approx. 3.4 mL of
0.1 M solution of the aminosilane electron donors (0.00034 mol) of
Examples I-IX and allowed to stand for 5 minutes. Of this mixture, 35 mL
was added to a flask. Then 0.0129 g of FT4S solid catalyst component (a
titanium halide and electron donor supported on an active MgCl.sub.2
compound catalyst component commercially available from Montell Italia
SpA) was added to the flask and mixed by swirling for a period of 5
minutes. The catalytic complex thus obtained was introduced, under an
argon purge, into the above polymerization reactor at room temperature.
The remaining hexane/TEAL/silane solution was then drained from the
addition funnel to the flask, the flask was swirled and drained into the
reactor and the injection valve was closed.
The polymerization reactor was slowly charged with 2.2 L of liquid
propylene, while agitating, and 0.25 mole percent of H.sub.2. Then the
reactor was heated to 70.degree. C. and polymerization was commenced for
about 2 hours at constant temperature and pressure. After about 2 hours
agitation was stopped and the remaining propylene was slowly vented. The
reactor was heated to 80.degree. C., purged with argon for 10 minutes and
then cooled to room temperature and opened. The polymer was removed and
dried in a vacuum oven at 80.degree. C. for 1 hour before testing was
performed.
Unless otherwise specified, the intrinsic viscosity of the polymers, IV, is
measured in decalin at 135.degree. C. using a Ubbelohde type viscometer
tube by the method of J. H. Elliot et al., J. Applied Polymer Sci., 14,
2947-63 (1970). The mileage of the polymer is calculated according to the
formula:
##EQU1##
The percent xylene solubles at room temperature, % XSRT, of the polymer
was determined by dissolving 2 g of polymer in 200 ml of xylene at
135.degree. C., cooling in a constant temperature bath at 22.degree. C.
and filtering through fast filter paper. An aliquot of the filtrate was
evaporated to dryness, the residue weighed and the weight % soluble
fraction calculated.
Test results are set forth in Table 1 below.
TABLE 1
__________________________________________________________________________
% Mileage
Intrinsic
Melt Flow
XSRT
Aminosilane
Hydrogen
(g pp/g cat)
Viscosity (dL/g)
Rate (wt %)
P.I.
__________________________________________________________________________
Example I
0 22,353
4.94 0 2.19
0.2 47,168
3.7 0.56 3.03
5.6
0.75 57,767
2.63 3.18 1.93
1.5 56,486
1.83 12.49
2.57
4.5
2.5 55,208
1.57 31.27
2.31
4.6
5 54,222
1.16 98.89
2.6 4.6
Example II
0 21,329
9.4 0.02 2.79
0.2 45,487
3.48 0.75 2.21
5.5
0.75 57,714
2.4 4.29 2.18
1.5 54,528
1.82 12.66
2.47
5.2
2.5 53,555
1.48 34.54
2.79
4.9
5 56,153
1.25 96.27
2.75
4.6
Example III
0 19,805
6.47 0.01 3.39
0.2 43,750
2.39 4.3 2.45
5.0
0.75 51,386
1.56 25.23
2.24
1.5 46,818
1.22 88.09
2.74
4.4
2.5 43,297
1.01 213.06
2.86
4.4
Example IV
0 20,952
11.1 0.01 3.43
0.2 47,211
2.78 1.6 2.1 4.8
0.75 52,444
1.95 9.03 2.42
1.5 49,285
1.54 30.43
2.42
4.5
2.5 46,333
1.22 77.65
2.15
4.4
5 42,755
0.91 307.31
2.85
4.5
Example V
0 14,601
7.72 0.03 5.15
0.2 33,465
2.28 5.04 3.5 6.6
0.75 41,456
1.58 25.3 2.87
1.5 42,391
1.26 75.38
2.95
4.5
2.5 42,173
1.11 153.6
3 4.7
Example VI
0 18,216
6.12 0.03 4.49
0.2 45,398
2.04 6.82 2.85
4.5
0.75 54,857
1.5 29.56
2.77
1.5 46,923 74.7 2.94
4.3
2.5 48,620 96.4 2.85
4.3
5 42,058 551 2.97
4.4
Example VII
0 17,939
6.88 0.03 3.37
0.2 37,804
2.05 14.2 2.55
4.4
0.75 44,151
1.47 32.63
2.45
1.5 37,378 101.4
2.64
4.3
2.5 39,754 149.3
2.41
4.3
5 36,090 694.8
2.83
4.2
Example VIII
0 19,000
10.23 0.01 2.95
0.2 40,280
2.57 2.77 2.15
N.D.*
0.75 47,407
1.93 11.75
2.2
Example IX
0 19,655
5.16 0.11 8.27
0.2 36,272
2.08 13.24
7.29
4.4
0.75 40,540
1.21 75 5.94
1.5 38,867 179.1
5.86
4.6
2.5 36,581 344.4
8.48
4.5
5 33,966 1,598
6.55
4.4
__________________________________________________________________________
*N.D. Not Done
Comparative Example
The polymerization procedure of Example X was followed, using 0.25% of
hydrogen and a 20/1 ratio of Al/Si, and with
3,3,3-trifluoropropyl(4-methylpiperidyl)-dimethoxysilane used as the
aminosilane. The catalyst exhibited a mileage of 43,900 grams of
polypropylene per gram of catalyst. The resulting polymer had an intrinsic
viscosity of 2.35, a XSRT of 1.51% and a polydispersity index of 4.22.
Other features, advantages and embodiments of the invention disclosed
herein will be readily apparent to those exercising ordinary skill after
reading the foregoing disclosures. In this regard, while specific
embodiments of the invention have been described in considerable detail,
variations and modifications of these embodiments can be effected without
departing from the spirit and scope of the invention as described and
claimed.
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